(12) United States Patent (10) Patent No.: US 9,409,853 B2 Schuch Et Al

USOO9409853B2

(12) United States Patent (10) Patent No.: US 9,409,853 B2 Schuch et al. (45) Date of Patent: Aug. 9, 2016

(54) POLYGLYCEROL PARTIAL ESTERS, 69/732 (2013.01); A61 K 2800/30 (2013.01); PREPARATION AND USE THEREOF A61 K 2800/49 (2013.01) (58) Field of Classification Search (71) Applicants: Dominik Schuch, Haan (DE); Wolfgang CPC ...... C07C 69/52; C07C 67/08; C07C 69/732; Berkels, Bottrop (DE); Oliver Springer, A61K 8/375; A61K 8/39; A61K 8/86; A61O Wesel (DE); Christian Hartung, Essen 1/14: A01O 5/02: A01O 15700; A01O 19/10 (DE); Hilke Condé, Gladbeck (DE): USPC ...... 554/219 Baerbel Klann-Metz, Essen (DE) See application file for complete search history. (56) References Cited (72) Inventors: Dominik Schuch, Haan (DE); Wolfgang Berkels, Bottrop (DE); Oliver Springer, U.S. PATENT DOCUMENTS Wesel (DE); Christian Hartung, Essen 5,840,943 A 11/1998 Ansmann et al. (DE); Hilke Condé, Gladbeck (DE): 6,581,613 B2 6/2003 Berkels et al. Baerbel Klann-Metz, Essen (DE) 7,851,511 B2 12/2010 Allefet al. 7,906,664 B2 3/2011 Allefet al. 8,211,972 B2 7/2012 Meyer et al. (73) Assignee: EVONIK DEGUSSA GMBH, Essen 8,642,525 B2 2/2014 Herrwerth et al. (DE) 2013,0071340 A1 3/2013 Wenk et al. 2013/0171087 A1 7/2013 Herrwerth et al. (*) Notice: Subject to any disclaimer, the term of this 2013/0204021 A1 8/2013 Hartung et al. patent is extended or adjusted under 35 2013/0281552 A1 10/2013 Nilewski et al. U.S.C. 154(b) by 4 days. 2014f0072521 A1 3/2014 Meyer et al. (21) Appl. No.: 14/564,408 FOREIGN PATENT DOCUMENTS EP 1197.559 4/2002 (22) Filed: Dec. 9, 2014 EP 2273966 1, 2011 JP 2008119568 5, 2008 (65) Prior Publication Data WO WO2004O41769 5, 2004 WO WO2007027447 A1 3, 2007 US 2015/O315123 A1 Nov. 5, 2015 WO WO2009 1383.06 A1 11 2009 OTHER PUBLICATIONS (30) Foreign Application Priority Data Wilson, R., et al., “Overview of the Preparation, Use and Biological Dec. 5, 2013 (DE) ...... 10 2013 224957 Studies on Polygycerol Polyricinoleate (PGPR)”. Food and Chemi cal Toxicology, Jan. 1998, p. 721, 36. European Search Report dated Apr. 23, 2015, received in a corre (51) Int. Cl. sponding foreign application. C07C 59/00 (2006.01) Schrader, K. et al., “Grundlagen and Rezepturen der Kosmetika' C07C 69/52 (2006.01) “Principles and Formulations of Cosmetics”, 1989, 2nd edition, p. C07C 67/08 (2006.01) 329 to 341, Hüthig BuchVerlag Heidelberg. A6 IK S/37 (2006.01) Cassel, S., et al., “Original Synthesis of Linear, Branched and Cyclic C07C 69/732 (2006.01) Oligoglycerol Standards'. European Journal of Organic Chemistry, A6 IK 8/39 (2006.01) Mar. 2001, vol. 2001, Issue 5, pp. 875-896. A61O I/14 (2006.01) Primary Examiner — Deborah D Carr A61O 5/02 (2006.01) (74) Attorney, Agent, or Firm — Scully, Scott, Murphy & A61O 15/00 (2006.01) Presser, P.C. A6 IK 8/86 (2006.01) (57) ABSTRACT A61O 19/10 (2006.01) (52) U.S. Cl. Polyglycerol partial esters of a specific composition which CPC ...... C07C 69/52 (2013.01); A61K 8/375 are capable of solubilizing very hydrophobic, oil-soluble sub (2013.01); A61K 8/39 (2013.01); A61K 8/86 stances in aqueous solution are provided. The preparation and (2013.01); A61O 1/14 (2013.01); A61O 5/02 use of these polyglycol ether-free solubilizers in cosmetic (2013.01); A61O 15/00 (2013.01); A61O 19/10 formulations are also disclosed. (2013.01); C07C 67/08 (2013.01); C07C 18 Claims, No Drawings US 9,409,853 B2 1. 2 POLYGLYCEROL PARTIAL ESTERS, long-chain triglycerides, in water or to solubilize a cosmetic PREPARATION AND USE THEREOF formulation, which is not possible using the products based on polyglycerol esters available to date. FIELD OF THE INVENTION A further advantage of the present invention is that the polyglycerol partial esters described herein may be prepared The present invention relates to polyglycerol partial esters exclusively from renewable raw materials in contrast to poly of a specific composition which are capable of Solubilizing ethoxylated triglycerides. very hydrophobic, oil-soluble Substances in aqueous solu A yet further advantage of the present invention is that the tion. The present invention also relates to the preparation and polyglycerol partial esters described herein are liquid, and use of these polyglycol ether-free solubilizers in cosmetic 10 thus readily processable, in contrast to polyethoxylated trig formulations. lycerides. An even further advantage of the present invention com PRIOR ART pared to the polyethoxylated triglycerides is that the polyg Non-ionic Surfactants having hardly any foam-generating 15 lyceryl esters described herein lead to particularly clear dis effect are usually employed as solubilizers of oil-soluble, persions of the oil in the water, and also no cloudiness occurs hydrophobic substances in water. on storage, in contrast to polyethoxylated triglycerides (PEG Polyethoxylated triglycerides, particularly based on castor 40 hydrogenated castor oil). oil, e.g., PEG-40 hydrogenated castor oil, are used as standard Another advantage of the present invention is that formu solubilizers. The latter is virtually able to clearly solubilize lations may be provided that are polyglycol ether-free. oil-soluble substances of a wide variety of structures and A further advantage of the polyglycerol partial esters hydrophobicity in water. Polyglycol ether-free polyglycerol described herein is that the polyglycerol partial esters of the partial esters have also been used for some years as alternative present invention can produce a pleasant skin sensation in solubilizers. cosmetic formulations. The disadvantage of all polyglycerol partial esters avail 25 Another advantage of the polyglycerol partial esters able to date is that their use as solubilizers of oil-soluble described herein is that the polyglycerol partial esters of the Substances in water cannot cover as wide a Substance spec present invention exhibit only a very low foam formation on trum as the previously mentioned polyethoxylated triglycer stirring in water. ides. The polyglycerol esters are thus mainly suitable for A further advantage is that the polyglycerol partial esters solubilizing 'small molecules such as, for example, short 30 described herein show only a very low effect on foamability chain terpenes. In contrast, oils based on fatty acids and and foam quantity in Surfactant formulations, but the foam triglycerides of long-chain fatty acids such as jojoba oil. creaminess can, however, improve. almond oil, soybean oil or avocado oil cannot, to date. be Another advantage is that the polyglycerol partial esters clearly solubilized in water using the commercial products described in the present invention may lead to attenuation of based on polyglycerol partial esters. 35 the skin irritancy in Surfactant formulations. JP 2008-119568 describes the use of polyglycerol partial A further advantage of the polyglycerol partial esters esters as solubilizers of oils in which the polyglycerol partial described herein is that the polyglycerol partial esters of the esters are based on mixtures of saturated fatty acids having 8 present invention can have a stabilizing effect in emulsions. to 22 carbonatoms and unsaturated fatty acids having 16 to 22 A further advantage of the inventive products is that they carbon atoms, wherein the molar ratio of Saturated to unsat 40 are relatively stable to oxidation and more stable with respect urated fatty acids is in a range of 0.2 to 0.8 to 0.8 to 0.2. In to color, odor and appearance. addition, polyglycerol partial esters of polyricinoleic acid may be admixed with this polyglycerol partial ester. DETAILED DESCRIPTION OF THE INVENTION SUMMARY OF THE INVENTION 45 The present invention provides polyglycerol partial esters of general formula I One object of the present invention is to provide solubiliz ers based on polyglycerol partial esters which, in contrast to the products available on the market to date, are able to clearly general formula I solubilize, in particular, hydrophobic, oil-soluble Substances, 50 Such as long-chain triglycerides, in water and to Solubilize RO O cosmetic formulations. It has been Surprisingly found that the polyglycerol partial OR2 esters described in the present invention are able to rectify the disadvantages of the prior art and thus enable to achieve the 55 where object of the present invention mentioned above. n=2 to 16, preferably 4 to 14, particularly preferably 5 to 11, In one embodiment of the present invention, polyglycerol R", R, R-independently of one another, identical or differ partial esters are provided which are prepared from polyglyc ent, selected from H. R. and erol by esterification of a specifically selected fatty acid mix R, where ture. The products are able to clearly solubilize very hydro 60 R=Saturated or unsaturated acyl residue having 6-22 carbon phobic, oil-soluble Substances, such as long-chain atoms, preferably 8-18 carbon atoms, comprising no triglycerides, in water or to solubilize a cosmetic formulation. hydroxyl groups, The preparation and use of these solubilizers in cosmetic R=Saturated or unsaturated acyl residue having 6-22 carbon formulations is also part of this invention. atoms, preferably 14-22 carbon atoms, comprising at least An advantage of the present invention is that the polyglyc 65 one hydroxyl group or an acyl residue of an oligomer of erol partial esters described herein are able to clearly solubi saturated or unsaturated acyl residues having 6-22 carbon lize strongly hydrophobic, oil-soluble Substances, such as atoms, preferably 14-22 carbon atoms, comprising at least US 9,409,853 B2 3 4 one hydroxyl group, in which the acyl residue of the oli noyland hydroxystearoyl residues, based on all R residues in gomer preferably has 26 to 66 carbon atoms, the polyglycerol partial ester, in which it is preferred that the characterized in that the molar ratio of the acyl residues R to mixture of ricinoyl and hydroxy Stearoyl residues has a molar R is in a range of 95.5 to 5:95, preferably 85:15 to 15:85, ratio of ricinoyl to hydroxystearoyl residues in a range of 100 particularly preferably 85:15 to 50:50. to O.1 to 50 to 50. A person skilled in the art is aware that the polyglycerol As an alternative, R is preferably selected from ricinoyl base skeleton present in general formula I, owing to its poly residues. meric property, represents a random mixture of various com Preferred polyglycerol partial esters according to the pounds. Polyglycerol may have formed ether bonds between invention are characterized in that the weight ratio of the two primary, one primary and one secondary and also two 10 polyglyceryl residue to the sum total of the acyl residues R' secondary positions of the glycerol monomers. For this rea and R is 85:15 to 55:45, preferably 80:20 to 60:40, particu son, the polyglycerol base skeleton does not usually consist larly preferably 75:25 to 65:35. exclusively of linearly linked glycerol units, but may also Preferred polyglycerol partial esters according to the comprise branches and rings. For details see, e.g., “Original invention are further characterized in that the molar ratio of synthesis of linear branched and cyclic oligoglycerol stan 15 saturated to unsaturated acyl residues in the sum total of all R' dards”, Cassel et al., J Org. Chem. 2001, 875-896. and R residues is 99:1-1:99, preferably 95:5-50:50, particu Structures of this kind are covered in this respect in the larly preferably 90:10-60:40. simplified, general formula I. The polyglycerol partial esters of the present invention can From the term “the molar ratio of the acyl residues R* to R be prepared by classical esterification and transesterification is in a range of 95:5 to 5:95”, it is clear that residues RandR methods, preferably by the inventive method described here are present in the polyglycerol partial esters according to the inafter. invention. The present invention further relates to a method for pre Preferred polyglycerol partial esters according to the paring polyglycerol partial esters comprising the method invention are characterized in that they comprise structures of 25 steps of: general formula 1) each having at the same time at least one A) providing a polyglycerol having a mean degree of poly R" residue and one R residue. merisation n=2 to 16, preferably 4-14, particularly pref The acyl residues R and R can be randomly attached to erably 5-11, the polyglycerol base skeleton both via primary and via sec B) acylation of some of the hydroxyl groups of the polyg ondary hydroxyl groups. 30 lycerol with All conditions such as, for example, pressure and tempera at least one first carboxylic acid derivative of one or more first, ture, if not stated otherwise, are standard conditions (20°C., saturated or unsaturated carboxylic acids having 6-22 car 1 bar). Percentages are indicated, if not described otherwise, bon atoms, preferably 8-18 carbon atoms, comprising no in mass percent. hydroxyl groups and The degree of polymerisation in can thus be determined, 35 at least one second carboxylic acid derivative of one or more whereby the hydroxyl number of the polyglycerol used for second, Saturated or unsaturated carboxylic acids having the synthesis of the inventive ester is determined, in which the 6-22 carbon atoms, preferably 14-22 carbon atoms, com mean degree of polymerisation n is related to the hydroxyl prising at least one hydroxyl group or an oligomer of the number of the polyglycerol on which it is based via the second carboxylic acid, wherein the oligomer preferably following equation: 40 has 26 to 66 carbon atoms, in which the carboxylic acid derivatives are selected from carboxylic acids and carboxylic esters, wherein triglycer 2000. M (KOH) - M (Water) ides are preferred as carboxylic esters in accordance with OHZ the invention, 1000. M (KOH) M (Glycerol) - M (Water)- 45 wherein the molar ratio of the acyl residues of the first car OHZ boxylic acid derivative used in method step B) to those of the second carboxylic acid derivative is in a range of 95:5 where M=molar mass; OHZ-hydroxyl number of the free to 5:95, preferably 85:5 to 15:85, particularly preferably polyglycerol. 85:15 to 50:50. Alternatively, the degree of polymerisation in can also be 50 The carboxylic acid derivatives preferably used in the determined by determining the hydroxyl number of the method according to the invention are fatty acid derivatives. polyglycerol obtained after complete ester hydrolysis. In the method according to the invention, therefore, in Suitable methods for determining the hydroxyl number are method step B) particularly those according to DGFC-V 17a (53), Ph. Eur. at least one first carboxylic acid and at least one second 2.5.3 Method A and DIN 53240. 55 carboxylic acid, The acyl residues Rand Rare preferably acyl residues of at least one first carboxylic ester and at least one second fatty acids. R* and R may also represent mixtures of such carboxylic acid, acyl residues, particularly technical mixtures such as, in the at least one first carboxylic acid and at least one second case of R', coconut fatty acid cuts. carboxylic ester, For R', it is with particular preference that at least 50 mol 60 at least one first carboxylic ester and at least one second %, preferably at least 75 mol %, of the R acyl residues are carboxylic ester, selected from capryloyl, caproyl and lauroyl residues, based at least one first carboxylic acid and at least one first carboxy on all R residues in the polyglycerol partial ester. lic ester and at least one second carboxylic acid, R is particularly preferably selected from ricinoyl and at least one first carboxylic acid and at least one first carboxy hydroxy Stearoyl residues, their oligomers and mixtures 65 lic ester and at least one second carboxylic ester, thereof, particularly preferably at least 90 mol % of the R at least one first carboxylic acid and at least one second acyl residues comprise ricinoyl residues or a mixture of rici carboxylic acid and at least one second carboxylic ester, US 9,409,853 B2 5 6 at least one first carboxylic ester and at least one second positions, hair treatments, hair arranging compositions, hair carboxylic acid and at least one second carboxylic ester, styling compositions, blow-drying lotions, setting foams, O hair treatments, leave-in conditioners, hair Smoothing com at least one first carboxylic acid and at least one first carboxy positions, shine improving compositions and compositions lic ester and at least one second carboxylic acid and at least for colouring the hair. The present invention therefore also one second carboxylic ester, relates to such uses. may be used. The present invention thus also provides care and cleaning A preferred method according to the invention is charac formulations, in particular for skin and skin appendages, terized in that at least 50 mol %, preferably at least 75 mol%. comprising polyglycerol partial esters according to the inven of the first carboxylic acids are selected from caprylic acid, 10 capric acid and lauric acid, based on the acyl residues of all tion. the first carboxylic acid derivatives. The term "care formulation' is herein understood to mean It is preferred in accordance with the invention, in the a formulation which satisfies the purpose of restoring an method according to the invention, that at least 90 mol% of object to its original form, of reducing or avoiding the effects the second carboxylic acids are selected from ricinoleic acid 15 of external influences (e.g., time, light, temperature, pressure, and hydroxy Stearic acid, based on the acyl residues of all the Soiling, chemical reaction with other reactive compounds that second carboxylic acid derivatives. come into contact with the object) Such as ageing, Soiling, A preferred method according to the invention is charac material fatigue, bleaching or even of improving desired posi terized in that at least 90 mol% of the second carboxylic acids tive properties of the object. For the last point, mention may comprise ricinoleic acid and/or hydroxyStearic acid, wherein be made for example of a shine of the object under consider the second carboxylic acids preferably have a molar ratio of ation. ricinoleic acid residues to hydroxy Stearic acid residues in a Cosmetic care and cleaning formulations according to the range of 100 to 0.1 to 50 to 50, based on the acyl residues of invention can, for example, comprise at least one additional all the second carboxylic acid derivatives. component selected from the group of: Alternatively, the second carboxylic acid derivative is pref 25 emollients, erably selected from ricinoleic acid or castor oil. emulsifiers, It is preferred, in the method according to the invention, thickenerS/viscosity regulators/stabilizers, that the weight ratio of the polyglycerol to the calculated sum antioxidants, total of the acyl residues of the first and second carboxylic hydrotropes (or polyols), acid derivatives used is 85:15 to 55:45, preferably 80:20 to 30 solids and fillers, 60:40, particularly preferably 75:25 to 65:35. pearlescence additives, A preferred method according to the invention is charac deodorant and antiperspirant active ingredients, terized in that the molar ratio of the acyl residues of saturated insect repellents, to those of the unsaturated carboxylic acid derivatives used in Self-tanning agents, method step B) is 99:1-1:99, preferably 95:5-50:50, particu 35 preservatives, larly preferably 90:10-60:40. conditioners, The present invention furthermore relates to polyglycerol perfumes, partial esters, obtainable by the method according to the dyes, invention, wherein the preferred partial esters according to cosmetic active ingredients, the invention are those which are obtainable by the preferred 40 care additives, method according to the invention. Superfatting agents, The present invention further relates to formulations, par Solvents. ticularly cosmetic and pharmaceutical formulations, wherein Substances which can be used as exemplary representa particular preference is given to cosmetic formulations which tives of the individual groups are known to a person skilled in comprise at least one polyglycerol partial ester according to 45 the art and can be found, for example, in EP2273966A1. This the invention and/or at least one polyglycerol partial ester patent application is herewith incorporated as reference and obtainable by the method according to the invention. thus forms part of the disclosure. Particular preference is given to formulations which are As regards to further optional components and the amounts essentially polyglycol ether-free and essentially free of of these components used, reference is made expressly to the alkoxylated compounds. The term “essentially free of 50 relevant handbooks known to a person skilled in the art, e.g., alkoxylated compounds' and “essentially polyglycol ether K. Schrader, "Grundlagen and Rezepturen der Kosmetika free', in connection with the present invention, are under Fundamentals and Formulations of Cosmetics, 2nd edi stood to mean that the formulations have no notable amounts tion, pages 329 to 341, Hüthig Buch Verlag Heidelberg. of alkoxylated compounds or compounds comprising polyg The amounts of the particular additives are governed by the lycol ethers which exert a surface-active effect. This is par 55 intended use. Typical guide formulations for the respective ticularly understood to mean that these compounds are applications are known prior art and are contained for present in amounts of less than 1% by weight, preferably less example in the brochures of the manufacturers of the particu than 0.1% by weight, particularly preferably less than 0.01% lar basic materials and active ingredients. These existing for by weight, based on the total formulation, in particular no mulations can usually be adopted unchanged. If necessary, detectable amounts. 60 the desired modifications can, however, be undertaken with The polyglycerol partial esters of the present invention can out complication by means of simple experiments for the be used advantageously for preparing care and cleaning for purposes of adaptation and optimization. mulations, particularly for skin and skin appendages, such as Preferred formulation according to the invention comprise liquid Soaps, shower gels, oil baths, make-up removers or preferred polyglycerol partial esters according to the inven shampoos, shower gels, foam baths, liquid soaps, hair sham 65 tion as set out above or preferred polyglycerol partial esters poos, 2-in-1 shampoos, hair conditioners, permanent wave according to the invention obtainable by the method accord fixing Solutions, hair colouring shampoos, hair setting com ing to the invention as set out above. US 9,409,853 B2 7 8 It is preferred if the formulation according to the invention tinuously distilled off. After cooling to room temperature, the additionally comprise at least one oil-soluble Substance and reaction product was in the form of a turbid liquid. Water. 1.3. Preparation of Polyglycerol Partial Ester C: In the present invention, oil-soluble Substances are under Under a nitrogen atmosphere, 225 g of polyglycerol (hy stood to mean Substances having a log P (logarithm of n-oc droxyl number=935 mg KOH/g) were stirred with 47.3 g of tanol/waterpartition coefficient, also known as log Ki) of at caprylic/capric acid and 20.8 g of refined coconut fatty acid least 2. and 17.7 g of ricinoleic acid and 12.4 g of hydroxy Stearic acid Preference is given to oil-soluble substances having a log P at 240°C. until an acid number<0.5 mg KOH/g was achieved. of at least 5. Particular preference is given to oil-soluble The water formed during the course of the reaction was con Substances selected from the group comprising oils based on 10 tinuously distilled off. After cooling to room temperature, the fatty acids, triglycerides of long-chain fatty acids, cosmetic reaction product was in the form of a turbid liquid. ester oils, pure hydrocarbons such as jojoba oil, almond oil, 1.4. Preparation of Polyglycerol Partial Ester D: Soybean oil, avocado oil, olive oil, argan oil, rapeseed oil, Under a nitrogen atmosphere, 202 g of polyglycerol (hy Sunflower oil, neem oil, caprylic/capric acid triglyceride, shea 15 droxyl number=884 mg. KOH/g) were stirred with 37.7 g of butter, decyl cocoate, isopropyl palmitate, myristyl myristate caprylic/capric acid and 24.9 g of refined coconut fatty acid and isohexadecane. and 23.5g of ricinoleic acid and 12.4 g of hydroxy Stearic acid Particularly preferred formulations according to the inven at 240°C. until an acid number<0.5 mg KOH/g was achieved. tion comprise 0.1% by weight to 40% by weight, preferably The water formed during the course of the reaction was con 0.3% by weight to 35% by weight, particularly preferably tinuously distilled off. After cooling to room temperature, the 0.5% by weight to 10% by weight, of polyglycerol partial reaction product was in the form of a turbid liquid. ester according to the invention and/or polyglycerol partial 1.5. Preparation of Polyglycerol Partial Ester E: ester obtainable by the method according to the invention, Under a nitrogen atmosphere, 225 g of polyglycerol (hy 0.01% by weight to 40% by weight, preferably 0.1% by droxyl number=935 mg KOH/g) were stirred with 39.4 g of weight to 30% by weight, particularly preferably 0.2% by 25 caprylic/capric acid and 23.0 g of refined coconut oil and 41.5 weight to 2% by weight, of oil-soluble substance and 10% by g of castor oil at 240°C. until an acid number<0.5 mg KOH/g weight to 98% by weight, preferably 20% by weight to 95% was achieved. The water formed during the course of the by weight, particularly preferably 45% by weight to 90% by reaction was continuously distilled off. After cooling to room weight, of water. temperature, the reaction product was in the form of a turbid The present invention also relates to the use of at least one 30 liquid. polyglycerol partial ester according to the invention and/or at 1.6. Preparation of Polyglycerol Partial Ester F: least one polyglycerol partial ester obtainable by the method Under a nitrogen atmosphere, 225 g of polyglycerol (hy according to the invention for solubilizing at least one oil soluble substance in water, wherein it is preferable in accor droxyl number=935 mg KOH/g) were stirred with 39.4 g of dance with the invention that preferred polyglycerol partial 35 caprylic/capric acid and 23.0 g of refined coconut oil and 23.0 esters according to the invention as set out above or preferred g of castor oil and 14.2 g of castor wax at 240°C. until an acid polyglycerol partial esters according to the invention obtain number<0.5 mg KOH/g was achieved. The water formed able by the method according to the invention as set out above during the course of the reaction was continuously distilled are used. off. After cooling to room temperature, the reaction product The examples listed below describe the present invention 40 was in the form of a turbid liquid. by way of example, without any intention of restricting the 1.7. Preparation of Polyglycerol Partial Ester G: invention, the scope of application of which is apparent from In a first reaction, 225 g of polyglycerol (hydroxyl num the entirety of the description and the claims, to the embodi ber=935 mg KOH/g) were stirred under a nitrogen atmo ments specified in the examples. sphere with 38.0 g of caprylic acid and 60 g of castor oil at 45 240° C. until an acid number<0.5 mg KOH/g was achieved. EXAMPLES The water formed during the course of the reaction was con tinuously distilled off. Example 1 In a second reaction, 225 g of polyglycerol (hydroxyl num ber=1060 mg KOH/g) were reacted under identical reaction Preparing Inventive Polyglycerol Partial Esters 50 conditions with 41.0 g of capric acid, 23 g of castor oil and 1.1 Preparation of Polyglycerol Partial Ester A: 46.0 g of refined coconut oil. Under a nitrogen atmosphere, 225 g of polyglycerol (hy The two products were then combined and stirred at 90° C. droxyl number=935 mg KOH/g) were stirred with 39.4 g of until a clear, homogeneous mixture was formed, which, after caprylic?capric acid and 20.8 g of refined coconut fatty acid 55 cooling to room temperature, was in the form of a turbid and 22.1 g of ricinoleic acid and 15.5g of hydroxy Stearic acid liquid. at 240°C. until an acid number<0.5 mg KOH/g was achieved. The water formed during the course of the reaction was con Example 2 tinuously distilled off. After cooling to room temperature, the reaction product was in the form of a turbid liquid. 60 Preparing Non-Inventive Polyglycerol Partial Esters 1.2 Preparation of Polyglycerol Partial Ester B: Under a nitrogen atmosphere, 225 g of polyglycerol (hy 2.1. Preparation of Polyglycerol Partial Ester H: droxyl number=996 mg KOH/g) were stirred with 39.4 g of Under a nitrogen atmosphere, 394 g of polyglycerol (hy caprylic?capric acid and 20.8 g of refined coconut fatty acid droxyl number=1061 mg KOH/g) were stirred with 51.3 g of and 22.1 g of ricinoleic acid and 15.5g of hydroxy Stearic acid 65 caprylic/capric acid and 23.0 g of refined coconut fatty acid at 240°C. until an acid number<0.5 mg KOH/g was achieved. and 32.8g of oleic acid at 240° C. until an acid number<0.5 The water formed during the course of the reaction was con mg KOH/g was achieved. The waterformed during the course US 9,409,853 B2 10 of the reaction was continuously distilled off. After cooling to 41. Surprisingly, similar solubilizer-to-oil ratios are even room temperature, the reaction product was in the form of a achieved as with the polyether-containing standard solubi turbid liquid. lizer TAGATR) CH 40 and whose performance is to some extent even exceeded. Example 3 Non-Inventive, Commercial Comparative Examples Example 5

3.1. TEGOSOFTR) PC.41: Improved Dissolving Power of the Inventive Standard solubilizer, polyether-free. INCI: Polyglyceryl-4 10 caprate. Commercial product of Evonik Industries AG. Polyglycerol Partial Esters in Surfactant 3.2. NATRAGEMRS 150 NP-LQ-(CM): Formulations in Comparison to the Non-Inventive Solubilizer for oils, polyether-free. INCI: Polyglyceryl-4 Polyglycerol Partial Esters laurate/sebacate (and) polyglyceryl-4 caprylate/caprate (and) water. Commercial product of Croda. 15 In addition to the dissolving properties of the inventive 3.3. TAGATR) CH4O: polyglycerol partial esters for oil in water shown in example Standard solubilizer, polyether-containing. INCI: PEG-40 4, the dissolving powerfor oils in Surfactant formulations was Hydrogenated castor oil. Commercial product of Evonik also investigated. Industries AG. For this purpose, the respective solubilizer was mixed with The products described above were tested in cosmetic for 0.5 g of caprylic/capric triglycerides (TEGOSOFTR, CT, mulations below. Evonik Industries AG) at 60°C. for 5 min. The water was then The formulation constituents are named in the composi slowly added at 60° C. with stirring and the mixture was tions in the form of the generally recognized INCI nomen stirred for 10 min. The mixture was then cooled to 30°C. over clature using the English terms. All concentrations are given a period of 30 min. The mixture was then treated with the in the application examples in percent by weight. 25 Surfactants with stirring. Example 4 The proportion of solubilizer required to completely dis solve 0.5% of the oil in the respective surfactant system was Improved Dissolving Power of the Inventive investigated. Two Surfactant systems were used: a standard Polyglycerol Partial Esters in Aqueous Solutions in 30 lauryl ether sulphate/betaine mixture (Table 2) and a poly Comparison to the Non-Inventive Polyglycerol ether-free formulation (Table 3). In Table 4, the resulting Partial Esters mass ratios of solubilizer-to-oil which were required to obtain clear mixtures are Summarized. In order to investigate the dissolving power of the inventive polyglycerol partial esters, these were mixed with cosmetic 35 TABLE 2 oils and treated with water. The oils tested were avocado oil Formulation Y for assessment of the solubilizing properties in a (Supplier: Gustav Heess) and caprylic/capric triglycerides standard Surfactant System. (TEGOSOFTR, CT, Evonik Industries AG). The proportion of solubilizer required to completely dissolve 0.5% of the Solubilizer X% respective oil in water was investigated. For this purpose, the 40 TEGOSOFT (R) CT, Evonik Industries AG, O.S90 solubilizer (various amounts) was thoroughly mixed with the (INCI: Caprylic?capric triglycerides) oil (0.5 g) and then slowly treated with water (made up to 100 Water to 100.0% Texapon (R) NSO, BASF Cognis, 28%, 32.0% g) with stirring. The mixture was stirred for one hour at 45° C. (INCI: Sodium laureth Sulphate After cooling to 20°C., a “clear mixture” must not become TEGO (R) Betaine F50, Evonik Industries AG, 38%, 8.0% turbid again over a period of 1 week. 45 (INCI: Cocamidopropyl betaine) In Table 1, the resulting mass ratios of solubilizer to oil Polymer JR 400, Amerchol, O.2% which were required to obtain clear mixtures are Summarized. (Polyguatemium-10) Citric acid, 30% to pH 5.5 TABLE 1. 50 Solubilizer-to-oil ratio required for a clear Solution of the oil in water. TABLE 3 Caprylicicapric Formulation Z for assessment of the solubilizing properties in a Avocado oil triglycerides polyether-free surfactant System. Polyglycerol partial ester A 10:1 4:1 Polyglycerol partial ester E 8:1 4:1 55 Solubilizer X% Polyglycerol partial ester F 9:1 4:1 TEGOSOFT (R) CT, Evonik Industries AG, O.S9/o Polyglycerol partial ester G 11:1 5:1 (INCI: Caprylic?capric triglycerides) Polyglycerol partial ester H >20:1 9:1 Water to 100.0% (non-inventive) REWOTERIC (RAMC, Evonik Industries AG, 32%, 17.5% TEGOSOFT (RPC41 >20:1 16:1 (INCI: Sodium cocoamphoacetate) (non-inventive) 60 Plantacare 1200 UP, BASF Cognis, 50%, 8.8% TAGAT (R CH4O 6:1 6:1 (INCI: Lauryl glucoside) (non-inventive) Plantacare 818 UP, BASF Cognis, 51%, 2.4% (INCI: Coco glucoside) PERLASTAN (R) SC 25 NKW, Schill&Seilacher, 25%, 14.4% It is evident from the results in Table 1 that the inventive (Disodium sodium cocoylglutamate) polyglycerol partial esters A, E, F and G have distinctly better 65 Citric acid, 30% to pH 5.2 solubilizing properties than the polyether-free comparative examples polyglycerol partial ester Hand TEGOSOFTR PC US 9,409,853 B2 11 12 TABLE 4 The sensory test results are summarized in Table 6.

Solubilizer-to-oil ratio required for a clear solution of TEGOSOFT (R) TABLE 6 CT in the surfactant formulations. 5 Results of the handwashing test: TEGOSOFT (RCT in TEGOSOFT (RCT in Test formulation U V W formulation Y formulation Z Foaming behaviour 3.3 3.6 3.5 Foam volume 3.1 3.3 3.2 Polyglycerol partial ester A 6:1 8:1 Foam creaminess 2.9 4.1 3.7 10 Polyglycerol partial ester F 5:1 6:1 Skin feel during washing 2.9 3.1 3.0 Rinseability 3.3 3.8 3.7 NATRAGEM (RS 150 12:1 11:1 Skin Smoothness 2.1 2.8 2.4 NP-LQ-(CM) Skin softness 2.3 3.1 2.8 Skin smoothness after 3 min 3.1 3.8 3.6 (non-inventive) Skin softness after 3 min 2.9 3.7 3.4 TEGOSOFT (RPC41 12:1 14:1 15 (non-inventive) TAGAT (R CH4O 8:1 5:1 It is evident from the test results in Table 6 that the inventive (non-inventive) formulation V using the inventive polyglycerol partial ester G is Superior, Surprisingly, in all application properties in com parison to the comparative formulation W according to the The results in Table 4 show that the inventive polyglycerol prior art. In this light, the results of the inventive formulation partial esters A and F have distinctly improved solubilizer V can be designated as very good and show a distinct properties in comparison to the comparative products improvement compared to the prior art. NATRAGEMRS 150 NP-LQ-(CM) and TEGOSOFTR PC It is evident from the measurements that the inventive 41. Surprisingly, better results were also obtained to some 25 polyglycerol partial ester G informulation V led especially to extent with the inventive polyglycerol partial esters A and F a significant improvement specifically of the foam creami than with the polyether-containing product TAGATR) CH40. ness and also the skin Smoothness and the skin softness. Example 6 30 Further Formulation Examples Improved Skin Care Power and Foam Properties of The formulation examples given in the tables below show the Inventive Polyglycerol Partial Esters in exemplary representatives of a large number of possible com Surfactant Mixtures in Comparison to Non-Inventive 35 positions according to the invention. Polyglycerol Partial Esters If the preparation of the formulation requires the separate preparation or mixing of formulation constituents before To evaluate the skin care benefit and the foam properties of hand, this is termed multiphase preparation. If a two-phase the inventive polyglycerol partial ester G in aqueous Surfac preparation is required, the two phases are labelled A and B in tant formulations, a sensory handwashing test was conducted 40 the stated tables. In the case of three- or more-phase pro in comparison to the comparative example TEGOSOFT(RPC cesses, the phases are called A, B, C etc. Unless stated other 41 according to the prior art. wise, the data in the tables are data in % by weight. In the A group consisting of 10 trained test personnel washed following formulation examples, the data or % by weight are their hands in a defined manner and assessed foam properties based on the respective active Substance. Some products, and skin feel using a grading scale from 1 (poor) to 5 (very 45 however, are commercially available as solutions, especially good). in water, such that in these cases more of the commercial The products were tested in each case in a standardized products were used accordingly, depending on the active Surfactant formulation, using the standard Surfactant system COntent. of 9% active sodium laureth Sulphate and 3% active cocami 50 “Product example A to G” corresponds to the “polyglyc dopropyl betaine (Table 5). erol partial esters A to G of example 1.

TABLE 5 TABLE 7

Test formulations for the handwashing test: 55 Formulation for Wet Wipes Formulation examples U V W Butylene glycol 2.0% Glycerol 1.0% Texapon (R) NSO-IS, BASF Cognis, 28%, 32.0% 32.0% 32.0% Product example A 1.0% (INCI: Sodium laureth Sulphate) Silicone quaternium-22; Polyglycerol-3 caprate; O.S9/o TEGO (R) Betaine F50, Evonik Industries 8.0% 8.0% 8.0% Dipropylene glycol; Cocamidopropyl betaine AG, 38%, (INCI: Cocamidopropyl 60 Allantoin O.2% betaine) Maltodextrin O.S9/o NaCl 1.5% 1.5% 1.5% Chamomilla extract O.1% Citric acid O.2% O.2% O.2% Phenoxyethanol; Ethylhexyl glycerol O.7% Water, demineralized 58.3% 55.3% 55.3% Perfume C.S. Polyglycerol partial ester G (inventive) 3.0% Water to 100.0% TEGOSOFT (R) PC 41 (non-inventive) 3.0% 65 Citric acid, 30% to pH 5.5 US 9,409,853 B2 13 14 TABLE 8 TABLE 1 1-continued

Bath cream Bath oil Water to 100.0% Sodium laureth Sulphate 8.0% Product example E 2.0% Coco glucoside 4.0% Perfume (fragrance) O.S9/o Cocamidopropyl betaine S.0% PEG-40 Hydrogenated castor oil O.1% Product example B 1.0% Trideceth-9 O.2% PEG-18 Glyceryl oleate? cocoate 2.0% Sodium lauroamphoacetate O.S9/o PEG-40 Sorbitan peroleate 1.4% Benzophenone-4 O.2% Perfume (fragrance) O.2% 10 Cocamide MEA O.4% Argania spinosa kernel oil O.2% Propylene glycol O.S9/o Citrus aurantifolia (lime) oil O.2% Disodium EDTA O.1% Linalool O.1% Coumarin O.1% Sodium chloride O.S9/o Glycerol O.S9/o Glycerol O.4% Glycol distearate O.S9/o 15 Benzyl alcohol O.4% Styrene? acrylates copolymer O.2% Argania spinosa oil O.2% Tocopherol O.1% Sodium cocoylglutamate O.3% Preservative C.S. Phenoxyethanol O.2% Citric Acid to pH 5.2 Xanthan gum O.2% Carbomer O.2% Lactic acid O.3% Magnesium chloride O.1% TABLE 9 Coumarin O.1% Citric acid to pH 5.2 Shower cream Preservative C.S. Water to 100.0% 25 Glycerol 4.0% Sodium laureth Sulphate 4.0% Cocamidopropyl betaine 3.5% TABLE 12 Product example G 2.0% Coco glucoside 2.0% Shower cream Ricinus communis seed oil seed) O.S9/o 30 Glyceryl oleate O.S9/o Water to 100.0% Argania spinosa kernel oil O.1% Sodium laureth Sulphate 10.0% Butyrospermum parkii butter extract O.1% Glycerol 3.0% Limonene O.1% Cocamidopropyl betaine 3.0% Perfume (fragrance) O.2% Product example F 2.0% Acrylates/C10-30 alkyl acrylate crosspolymer O.2% Decylglucoside 1.5% Hydroxypropyl methylcellulose O.2% 35 Perfume C.S. Styrene? acrylates copolymer O.2% Glycine soya oil O.2% Sodium hydroxide O.2% Heianthus annuus seed oil O.1% Glycol distearate O.4% Lecithin O.2% Silica O.2% Coco glucoside O.S9/o Tocopherol O.1% Glyceryl oleate O.3% Preservative C.S. 40 Coumarin O.1% Citric acid to pH 5.2 Preservative C.S.

TABLE 10 TABLE 13 45 Shower oil Body shampoo Heianthus annuus seed oil 10.0% Phase A Product example F 3.0% Ricinus communis seed oil 10.0% Simmondsia chinensis (jojoba) seed oil O.7% MIPA-Laureth Sulphate 20.0% Perfume O.2% Product example A 15.0% 50 Phase B Sodium cocoamphoacetate 4.0% Laureth-4 O.S9/o Phase C Water to 100.0% Cocamide DEA O.9% Acrylates/C10-30 alkyl acrylate crosspolymer O.9% Perfume (fragrance) O.2% Phase D Sodium lauroyl methylisethionate 4.0% Print is amygdalus duticis oil O.8% Capryl capramidopropyl betaine 2.0% Argania spinosa kernel oil O.8% Citric acid 1.3% Water O.S9/o Phase E Water 10.0% 55 Preservative C.S. Polyguaternium-7 O.3% Citric acid to pH 5.5 Preservative C.S.

TABLE 11 60 TABLE 1.4 Bath oil Body shampoo Water to 100.0% Phase A Product example C 6.5% Sodium laureth Sulphate 7.0% Simmondsia chinensis (jojoba) seed oil O.4% Cocamidopropyl betaine 6.0% Perfume O.2% Cocamide DEA 2.5% 65 Phase B Water to 100.0% Sodium trideceth Sulphate 2.2% Phase C Sodium cocoamphoacetate 4.0% US 9,409,853 B2 15 16 TABLE 14-continued TABLE 1.8 Shampoo Body shampoo Phase: Product example C 2.0% Caprylicicapric triglyceride O.S9/o Phase D Water 30.0% Perfume O.2% Phase B Water to 100.0% Acrylates beheneth-25 methacrylate copolymer 2.0% Phase C Sodium lauryl Sulphate 9.0% Sodium lauroyl methylisethionate 4.0% Phase: Cocamidopropyl betaine 3.0% Disodium lauryl Sulphosuccinate 2.0% Phase E Cocamide MEA 1.9% 10 Xanthan gum O.2% Phase E Preservative C.S. Water 10.0% Phase F Water 10.0% Polyguatemium-10 O.2% Phase: Citric acid to pH 5.7 TABLE 1.5 Phase H Preservative C.S. 15 Shampoo Phase A Product example E 3.0% TABLE 19 Caprylicicapric triglyceride O.S90 Perfume O.2% Deo Phase B Water to 100.0% Phase A Product example E 3.0% Phase C Sodium cocoamphoacetate 7.0% Glycine Soia (soybean) oil O.2% Phase: Glycerol 1.0% Perfume O.1% Xanthan gum O.8% Phase B Phenoxyethanol O.S90 Water 25.0% Caprylylglycol O.2% Phase E Water 10.0% 25 Phase C Water SO.0% Acrylates beheneth-25 methacrylate copolymer 2.0% Hydroxyethyl cellulose 0.75% Phase F Water 10.0% Sodium hydroxide (10% in water) O.25% Phase D Aluminium chlorohydrate 19.0% Polyguaternium-10) O.2% Phase E Water to 100.0% Phase G Cocamidopropyl betaine S.0% Preservative C.S. 30 TABLE 20 TABLE 16 Cleansing Oil Shampoo Shampoo Water to 100.0% 35 Sodium laureth Sulphate 7.0% Phase A Product example E 8.0% MIPA-Laureth Sulphate 4.0% Argania spinosa kernel Oil O.S9/o Sodium chloride 3.2% Phase: Water to 100.0% Cocamidopropyl betaine 3.0% Phase C Perfume O.3% Product example E 3.0% Polyglyceryl-6 caprylate; Polyglyceryl-4 caprate; 2.0% Glycerol 2.5% Propylene glycol 40 PEG-18 Castor oil dioleate 2.0% Phase D Water 20.0% Propylene glycol; PEG-55 Propylene glycol oleate 2.0% Phase E Sodium laureth Sulphate 9.0% Laureth-5 carboxylic acid 1.0% Phase F Water 10.0% Perseagratissina (avocado) oil 1.0% Cocamidopropyl betaine 3.0% Polyglyceryl-6 caprylate; Polyglyceryl-4 caprate; O.9% PEG-120 methylglucose dioleate 1.0% Propylene glycol Phase G Water 10.0% 45 Sodium benzoate O.7% Sodium chloride O.7% Salicylic acid O.3% Polyguaternium-10 O.2% Linalool O.2% Phase H Citric acid to pH 5.5 alpha-Isomethyl ionone O.1% Phase I Preservative C.S. Limonene O.1% Zea mays (corn) germ oil O.2% 50 Argania spinosa oil O.1% Camelia oleifera seed oil O.1% TABLE 17 Sodium hydroxide O.3% Citric acid to pH 5.0 Shower gel Perfume, Dyes C.S.

Phase: Product example F 3.0% 55 Caprylicicapric triglyceride O.S90 Perfume O.2% TABLE 21 Phase B Water to 100.0% Phase C Sodium cocoamphoacetate 5.6% Pampering Oil Bath Phase D Lauryl glucoside 4.4% Phase E Coco glucoside 1.2% Water to 100% Phase F Sodium disodium cocoylglutamate 3.6% 60 Glycine soya oil 20.0% Phase G Water 10.0% Product example B 10.0% Glycerol O.7% Polyglyceryl-3 palmitate 4.5% Water 10.0% Glyceryl caprylate 4.5% Xanthan gum 2.0% Simmondsia chinensis seed oil 1.5% Phase H Citric acid to pH 6.0 Prints amygdalus dulcis (Sweet almond) oil 1.0% Phase I Preservative C.S. 65 Tritictim vulgare germ oil 1.0% Tocopherol O.2% US 9,409,853 B2 17 18 TABLE 21-continued TABLE 25 Shampoo for Children Pampering Oil Bath Water to 100% Sodium coco Sulphate 7.0% Limonene O.1% Decylglucoside S.0% Lactis Proteinum 3.5% Linalool O.1% Sorbitan caprylate 3.0% Citral O.1% Product example F 3.0% Glycerol 2.5% Dyes C.S. 10 Sodium lactate 2.5% Alcohol 2.0% Hydrolysed wheat protein O.7% Hydrolysed wheat starch O.7% TABLE 22 Sodium chloride O.9% Limonene O.1% Shower Cream 15 Citral O.1% Phenethyl alcohol O.1% Water to 100% Dyes C.S. Glycerol 7.59% Glycine soya oil 3.0% Laurylglucoside 3.0% Sodium coco Sulphate 3.0% TABLE 26 Product example C 2.5% Alcohol 1.5% Cream Soap Xanthan gum 1.5% Butyrospermum parkii butter extract 1.2% Water to 100% Sodium cetearyl Sulphate 1.0% Alcohol S.O% Sodium cocoylglutamate 1.0% Coco glucoside S.O% Disodium cocoylglutamate 1.0% 25 Glycerol S.O% Tocopherol O.1% Product example F 2.5% Heianthus annuus seed oil O.3% Disodium cocoylglutamate 2.0% Limonene O.1% Xanthan gum 1.5% Benzyl salicylate O.1% Citric acid to pH 5.5 Linalool O.1% Malva Sylvestris leaf extract 1.0% Dyes C.S. 30 Glyceryl oleate 1.0% Sodium cocoylglutamate O.7% Linalool O.1% Limonene O.1% TABLE 23 Dyes C.S. 35 Shower Gel

Water to 100% TABLE 27 Sodium coco Sulphate S.0% Glycerol S.0% Make-up Remover Laurylglucoside 4.0% Sodium lactate 2.5% 40 Sodium cocoamphopropionate S.0% Product example D 2.0% Propylene glycol 35.0% Polyglyceryl-4 caprate 2.0% Product example F 30.0% Sodium cocoylglutamate 2.0% Glycerol 30.0% Disodium cocoylglutamate 2.0% Preservative C.S. Alcohol 1.0% Prunus cerasus fruit extract 1.0% 45 Polyglyceryl-6 caprylate: Polyglyceryl-4 1.0% caprate; Propylene glycol TABLE 28 Limonene O.1% Coumarin O.2% Make-up Remover Linalool O.1% Citral O.1% 50 Cocamidopropyl betaine 8.0% Dyes C.S. Water 79.0% Product example E 3.0% Glycerol 10.0% Citric acid to pH 5.5 TABLE 24 Preservative C.S. 55 Liquid Soap Water to 100% TABLE 29 Glycerol 7.0% Alcohol 4.0% Solution for Wet Wipes Sodium coco Sulphate 3.0% Laurylglucoside 2.5% 60 Product example E 1.5% Product example E 2.0% Perfume O.2% Xanthan gum 1.5% Glycerol 2.0% Mangifera indica (mango) fruit extract O.7% Sodium lactate: Sodium PCA: Glycine; Fructose; Urea; O.2% Limonene O.1% Niacinamide; Inositol; Sodium benzoate; Lactic acid Linalool O.1% Water 95.6% Dyes C.S. 65 Preservative US 9,409,853 B2 19 20 TABLE 30 TABLE 35 Shower Creme Solution for Wet Wipes Water to 100% Ammonium lauryl Sulphate 10.0% Product example E 2.0% Product example D 2.0% Aloe barbadensis leaf juice 2.0% Isopropyl myristate O.3% Cocamidopropyl betaine 2.0% Phenoxyethanol; Methylparaben; Ethylparaben; O.2% Decylglucoside 1.0% Butylparaben; Propylparaben; Isobutylparaben Glycerol 1.0% 10 PrintiSamygdalus dulcis oil O.S9/o Perfume O.1% Glyceryl oleate O.3% Laurylglucoside O.3% Propylene glycol 3.0% Coco glucoside O.4% Water 94.0% Benzyl alcohol O.2% Benzoic acid O.3% Cetrimonium bromide O.1% 15 Dehydroacetic acid O.2% Sodium benzoate O.3% Potassium sorbate O.2% Tocopherol O.1% TABLE 31 Citric acid to pH 4.5 Perfume, Dyes C.S. O.W Make-up remover wipe

Phase A Ethylhexyl stearate; Phenoxyethanol; Polyglyceryl-4 4.0% laurate; Sorbitan laurate; Dilauryl citrate TABLE 36 Cetyl ricinoleate O.8% Shower Creme Phase B Water to 100.0% 25 Glycerol 1.5% Water to 100% Phase C Product example C 1.0% Sodium laureth Sulphate 8.0% Phase D Phenoxyethanol O.1% Product example F 3.0% Perfume Cocamidopropyl betaine 3.0% C.S. Glycerol 1.0% Preservative C.S. Glucose O.S9/o 30 Prints amygdalus dulcis oil O.7% Sodium chloride O.3% Polyguaternium-7 O.3% TABLE 32 Styrene? acrylates copolymer O.4% PEG-200 Hydrogenated glyceryl palmate; O.S9/o Micellar water PEG-7 Glyceryl cocoate 35 Citric acid to pH 5.5 Water to 100.0% Perfume, Dyes C.S. Product example D S.0% Glycerol 1.5% Disodium cocoamphodiacetate O.S9/o Disodium EDTA O.2% TABLE 37 Polyaminopropylbiguanide O.2% 40 Citric acid, 30% to pH 5.5 Care shower

Water to 100% Sodium laureth Sulphate 9.0% TABLE 33 Sodium hydroxypropyl starch phosphate 2.5% 45 Product example E 2.0% Micellar Solution Cleanser Cocamidopropyl betaine 2.0% Petrolatum 1.0% Water to 100.0% Sodium cocoylglycinate 1.0% Butylene glycol S.0% Lauric acid O.S9/o Coco glucoside 2.0% Sodium lauroylisethionate O.S9/o Product example D 2.0% 50 Glycerol O.4% Glycerol 1.0% Heianthus annuus seed oil O.3% Allantoin O.1% Olea europaea fruit oil O.2% Cistus incanus extract; Maltodextrin O.2% Sodium chloride O.4% Perfume O.2% Stearic acid O.S9/o Citric acid, 30% to pH 5.5 Guar hydroxypropyltrimonium chloride O.2% Sodium Cocoylisethionate O.1% 55 Tetrasodium EDTA O.1% Alumina O.1% TABLE 34 Citric acid to pH 5.5 Perfumes, Dyes, Preservatives C.S. Cleansing Water Water to 100.0% 60 Product example E 2.5% TABLE 38 Phenoxyethanol; Ethylhexylglycerol O.9% Caprylicicapric triglyceride O.S9/o Shower Creme Glycerol O.S9/o Disodium EDTA O.2% Water to 100% Citric acid, 30% to pH 5.5 65 Sodium coco Sulphate 15.0% Glycerol 3.5% US 9,409,853 B2 21 22 TABLE 38-continued TABLE 38-continued Shower Creme Shower Creme Product example F 3.5% Tocopherol O.1% Glycine Soya oil O.S9/o 5 Heianthus annuus seed oil O.1% Coco glucoside O.8% Alcohol O.S9/o Caprylicicapric triglyceride O.2% Citral O.1% Xanthan gum O.8% Geraniol O.1% Print is amygdalus dulcis oil O.1% Limonene O.1% Simmondsia chinensis seed oil O.1% Linalool O.1% Sodium cocoylglutamate O.3% 10 Citric acid to pH 5.8 Disodium cocoylglutamate O.S9/o Perfume, Dyes C.S. Sodium cetearyl Sulphate O.2%

TABLE 39 Further formulation examples

Water to 100% Product example D 3.0% 4.0% S.5%. 1.0% 3.0% 3.0% S.0% 4.0% 3.5% 3.0% Sodium laureth Sulphate 9.0% 8.0% 9.0% Sodium lauryl Sulphate — 6.0% — — 3.5% — Cocamidopropyl betaine 2.0% 3.0% 7.0% S.0% 6.0% 2.0% 7.0% Sodium cocoamphoacetate 3.0% - - 1.5% 4.5% - 3.0% - 3.5% - Laurylglucoside 3.5% S.0% 3.0% 7.0% Coco glucoside — 2.0% — 1.5%. 1.0% S.5% 2.5% 2.0% Sodium cocoylglutamate 1.0% 1.7% S.0% 0.5% Stearic acid — 1.0% — - 0.1% 3.5% Glycerylglucoside — 0.3% — — 0.3% – 0.2% — Sucrose cocoate O.5% - 1.0% 1.0% O.3% O.2% 1.0% 1.0% 1.0% Glycerol O.S90 1.0% O.S90 0.3% O.4%. 1.5%. 1.0% 0.5%. 1.0% PEG-7 Glyceryl cocoate - 0.3% O.S9/o Trideceth-9 - 0.2% O.2% Polysorbate 20 — 0.5% — - 0.3% 0.2% PEG-40 Hydrogenated castor — 0.3% – 0.5% — — 1.0% — oil PEG-6 Caprylic?capric O.3% O.2% 0.2% glycerides Polyglyceryl-4 caprate - 2.0% - 0.5% - O.5% - O.5% Polyguaternium-10 — 0.2% — 0.1% — — 0.2% 0.2% — Hydroxypropyl guar O.2% 0.3% O2% O2% 0.2% O2%. O.1% hydroxypropyltrimonium chloride Silicone quaternium-22 - 0.3% O.3% Dimethicone — 0.3% — — 0.1% — Amodimethicone — 0.1% – 0.1% 0.1% — — 0.5% — Argania spinosa oil - 0.2% 0.1% 0.1% 0.2% Print is amygdalus duticis oil O.2% 0.2% O.3% 0.1% - 0.2% 0.2% Olea europaea fruit oil O.2% 0.1% — 0.1% – 0.2% 0.1% — Butyrospermum parkii butter — 0.2% O.1% extract Perseagratissina oil — 0.1% — 0.1% 0.2% — Hydrogenated castor oil — 0.2% — 0.1% — - 0.1% 0.2% Glycol distearate — 0.5% — - O.5% - 0.3% 0.5% 0.5% Isostearamide MIPA: 1.0% — — 1.5% — - O.2% 1.0% O.5% Glyceryl laurate Cocamide DEA — 0.5% — — 1.0% — Sodium chloride O.3%. 12%. 1.0% O.5% - 1.0% - 1.0% - O.3% PEG-120 Methylglucose O.2%. 3.5%. 1.0% - 1.5% - — 0.5% — dioleate Xanthan gum - 0.5% 0.8% - 0.7% 2.0% 1.0% Cellulose - O.1% 0.1% O.1% O2% 0.1% Zinc pyrithione — 0.1% — — 0.1% — Benzophenone-4 - 0.1% 0.1% 0.1%. O.1% 0.1% 0.1% Tetrasodium EDTA O.1% 0.1% O.1%. O.1% — 0.1% — Caffeine — 0.1% 0.1% — — 0.1% 0.1% — Hydrolysed keratin — 0.1% — - 0.1% 0.2% 0.1% 0.1% Panthenol O.1% 0.1% 0.1% O.1%. O.1%. O.1% O.1%. O.1%. O.1% Citric acid to pH 5.5 Perfumes, Dyes, Preservatives C.S. US 9,409,853 B2 23 24 TABLE 40 Further formulation examples 40a 40b 40c 40d 40e 40f 40g 40h 40i 40 Water to 100% Product example F 9.0% S.O% S.0% 4.0% 4.0% 2.5%. 6.0% 4.0% 3.0% 3.0% Sodium lauryl Sulphate - 8.0% 8.0% - — 3.5% — Coco betaine - 5.0% - 5.5% - — 3.0% — Cocamidopropyl betaine — 3.0% — 5.0% — - 3.0% 2.0% Sodium cocoamphoacetate - 2.5%. 3.0% - 5.0% - 3.0% 4.0% Disodium lauryl 1.0% 1.2% — Sulphosuccinate Coco glucoside 3.0% S.0% 4.0% S.0% 1.0% 2.0% Sodium cocoylglutamate 2.5% 3.0% 4.5% 0.5% 2.5% 0.3% Stearic acid O.3% O.1% 0.5% Sodium cocoylglycinate - 5.0% - 3.5% - 2.0% 7.0% Sodium lauroyl methyl - 1.0% - 1.5% - 1.0% O.5% O.5% isethionate Sucrose cocoate O.5% O.4% - 1.0% - 0.2% 0.3%. 1.0% 0.3% Glycerol 1.5% 0.3% 0.5% 0.5% 0.3% 0.5%. 1.0% 0.5% 0.3%. 1.0% PEG-40 Hydrogenated castor — 1.0% — — 0.3% — oil Polyglyceryl-4 caprate O.5% - — 0.5% — 2.6% — — 1.1% — Polyduaternium-11 — 0.2% — — 0.1% — - 0.2% 0.3% Guar - O.3% 0.2% 0.2% O.3% 0.2% 0.1% 0.2% hydroxypropyltrimonium chloride Dimethicone — 0.3% — — 0.2% — Aminopropyl dimethicone - O.3% O.5% - — 0.3% — Heianthus annuus seed oil O.3% O.1% O.5% - 0.1% O.1% 0.2% 0.1% Olea europaea fruit oil O.2%. O.1% O2% O.2% 0.1% O.2% O.6% 0.2% PEG-3 distearate — 0.5% — — 0.5% — Acrylates/C10-30 alkyl O.5% - O.4% O.5% 0.4% — 0.5% — acrylate crosspolymer Sodium hydroxide, 25% O.6% O.6% O.8% 0.5% - — 0.7% — Cocamide MEA - O.8%. 1.0% 1.0% O.2% 0.6%. 1.0% O.3% Sodium chloride O.2% O.7% 0.2% O.2% 0.1% 1.0% O.2%. 1.0% Propylene glycol; PEG-55 — 2.5% — — 0.8% — Propylene glycol oleate Xanthan gum O.2% 0.2%. 1.5% 0.5% 1.8% 0.2%. 1.1% 0.9% Hydroxyethyl ethylcellulose 0.1% — — 0.1% – 0.1% 0.1% — Benzophenone-4 — 0.1% 0.2% — — 0.2% — 0.1% Menthol 0.1% — 0.1% — - O.1% O.1% 0.1% O.1% Caffeine — 0.1% — 0.1% — — 0.1% – 0.1% Benzyl alcohol 0.1% — — 0.1% — 0.1% — Coumarin O.1% O.1%. O.1% - 0.1% O.1% O.1% Hydrolysed wheat protein - O.1% 0.1% 0.1% O.2% 0.2% 0.1% Panthenol O.1%. O.1% O.1%. O.1%. O.1%. O.1% O.1% 0.1% Citric acid to pH 5.2 Perfumes, Dyes, Preservatives C.S.

TABLE 41 Further formulation examples

Water to 100% Product example E 3.5% 3.0% 2.5% 4.0% 3.0% 4.0% 6.0% 4.0% S.O% 4.0% MIPA-Laureth Sulphate 10.5% S.0% Sodium C14-16 olefin — 8.0% — — 3.5% — Sulphonate Coco betaine 4.0% - 5.5% - — 4.0% — 3.5% — Cocamidopropyl betaine 2.0% - 4.0% - 5.0% 5.0% - — 4.0% Sodium cocoamphopropionate - 1.0% - 2.0% - 1.5% 4.0% 2.0% 3.5% Coco glucoside 2.5% 2.5% 3.0% 4.5% 3.5% 2.0% 0.5% Sodium cocoylglutamate 1.5%. 1.0% 1.5%. 1.5%. 1.5% 0.8% 0.3% Laurie acid O.5% - — 1.0% – 2.0% — 4.5% Sodium cocoylglycinate — 2.5% — 5.0% — - O.8% 0.5% Sodium cocoyl sarcosinate O.7% 0.5% - 1.0% O.5% - Dicaprylylether O.S90 — 0.2% — Glycerol O.S90 O.3% 0.5%. 1.5% 0.4% 0.5%. 1.0% O.S90 O.3%. 1.0% Polysorbate 20 O.S90 — 0.5% — — 0.4% Polyglyceryl-4 laurate O.S90 — 0.4% 0.3% — — 0.5% — 1.1% — Polyguaternium-37 O.4% — 0.1% — — 0.2% 0.1% — US 9,409,853 B2 25 26 TABLE 41-continued Further formulation examples 41a. 41b 41c 41d 41e 41f 41g 41 h 41i 41j Hydroxypropyl guar O.2% 0.1% 0.2% — 0.3% – 0.2% — hydroxypropyltrimonium chloride Cassia 0.1% — — 0.2% — hydroxypropyltrimonium chloride Sodium hydroxypropyl starch O.2% — 0.4% — - 0.5% phosphate Hydroxypropyl methylcellulose O.2% — 0.2% 0.2% — — 0.2% — Dimethicone O.2% — 1.0% — — 0.3% — Aminopropyl dimethicone O.2% 0.4% — 0.5% — - 0.5% Palmitamidopropyltrimonium O.3% — 0.5% — — 0.4% — chloride Persea gratissina (avocado) oil O.1% 1.1% O.1% 0.2% 0.3% O.1% 0.1% Butyrospermum parkii butter O.2% — 0.1% — — 0.3% — extract Prints amygdalus duticis oil O.2% — 0.2% 0.2% — - 0.2% O.5% - Glycol distearate O.S90 O.7% - O.5% 0.8% - - O.4% 0.3% Carbomer O.3% - 0.5% O.7% 0.5% - Sodium hydroxide, 25% O.5% - - 0.7%. 1.0% - 0.8% Isostearamide MIPA: Glyceryl O.7% - 0.8% 0.3% 0.3% O.4% O.3% laurate Sorbitan Sesquicaprylate — 0.2%. 1.0% — - 0.4%. 1.0% - O.7% Sodium chloride O.8% - 0.3% 0.2% 0.5% - — 2.0% — PEG-18 Glyceryl O.8% — 0.6% — - O.9% oleate? cocoate Xanthan gum 1.0% 0.2%. 1.0% - 0.2% 0.3% — 0.2% Algin 0.2% — — 1.0% — — 1.2% — Caragenaan O.S90 — 0.3% — - O.3% 0.2% Silica O.1% — 0.1% — — 0.2% — - O.2% 0.1% Cetearyl alcohol O.2% - O.3% 0.2% - 0.3% Benzophenone-4 O.1% 0.1% O.2% 0.2% 0.2% — 0.1% Tetrasodium EDTA O.1% 0.1% O.1% 0.1% O.2% 0.1% O.2% 0.1% Octopirox O.2% — 0.1% — Zinc PCA — 0.1% — — 0.1% Creatine O.1% - 0.1% 0.1% 0.1%. O.1%. O.1% O.1% Hydrolysed collagen - 0.1% O.1% O.1%. O.1%. O.1% Salicylic acid O.1% — 0.1% 0.1% — - O.1% 0.1% Panthenol O.1% 0.1% O.1% 0.1% O.1% 0.1% O.1% 0.1% Lactic acid O.2% - 0.2% 0.1% 0.5% O.3% 0.2% PEG-14M O.3% — 0.4% — - 0.3% 1.2-Hexanediol O.3% — 0.3% – 0.2% — Citric acid to pH 5.5 Perfumes, Dyes, Preservatives C.S.

TABLE 42 TABLE 42-continued 45 List of raw materials used List of raw materials used INCI Trade name, company INCI Trade name, company 1.2-Hexanediol Hydrolite-6 841129, Symrise Benzyl alcohol Microcare BNA,THORPERSONAL Acrylates beheneth-25 Novethix L-10 Polymer, Lubrizol 50 Benzyl salicylate CARESeridefrizz SAS Intense, Cheemyunion methacrylate copolymer Quimica Ltda. Acrylates/C10-30 alkyl TEGO Carbomer 8410. SER, Evonik Butylene glycol Butylene Glycol, Oxea Corporation acrylate industries AG, 100% Butyrospermain parkii Cosmosil 600, International Cosmetic crosspolymer butter extract Science Centre Algin Hydagen 558 P, BASF Caffeine Caffeine, Merck KGaA? EMD Chemicals, Allantoin Allantoin, DSM Nutritional Products, Inc. 55 Inc. Aloe barbadensis leaf juice Aloe-Con UP 40, Florida Food Products Camelia oleifera seed oil Cameliia Sasanquia Oil, Ikeda Corporation IlC. Caprylylglycol Sensiva SC 10, Schilke& Mayr GmbH alpha-Isomethyl ionone alpha-Isomethylionone, Chemos GmbH Capryl capramidopropyl TEGO Betain 810, Evonik Industries AG, Alumina Aeroxide Alu C, Evonik Industries AG betaine 38% Aluminium chlorohydrate Locron L, Clariant Caprylicicapric triglyceride TEGOSOFT CT, Evonik Industries AG, Ammonium lauryl Sulphate Empicol AL 70, Albright & Wilson UK 60 100% Limited Carrageenan Genugel Carrageenan, CP Kelco Aminopropyl dimethicone ABIL(R) Soft AF 200, Evonik Industries Carbomer TEGO Carbomer 140, Evonik Industries Amodimethicone DC 949, Dow Corning, 100% AG, 100% Argania spinosa oil (Argania Argan Oil, DSM Nutritional Products Ltd. Cassia Formularbeginn spinosa kernel oil) hydroxypropyltrimonium Sensomer ST 250-Polymer, Lubrizol Benzophenone-4 Uvinul MS 40, BASF Corporation 65 chloride Formularende Benzoic acid OriStar HSB, Orient Stars LLC Cellulose Arbocel A300, J. Rettenmaier & Söhne US 9,409,853 B2 27 28 TABLE 42-continued TABLE 42-continued

List of raw materials used List of raw materials used INCI Trade name, company 5 NCI Trade name, company Cetearyl Alcohol TEGO Alkanol 1618, Evonik Industries sostearamide MIPA: ANTIL SPA 80, Evonik Industries AG, AG, 100% Glyceryl laurate OO% Cetyl ricinoleate TEGOSOFT CR, Evonik Industries AG, Lactic acid AEC Lactic Acid, A & E Connock, 100% Perfumery & Cosmetics Ltd. Cetrimonium bromide Rhodacquat M-242B/99, Rhodia Lactis proteinum AECWhey Protein, A & E Connock, Chamomilia recutita Recentia CR, AkzoNobel Global Personal 10 Perfumery & Cosmetics Ltd. (matricaria) extract Care Laureth-4 TEGO Alkanol L 4, Evonik Industries Citral Citral FF, Symrise AG AG, 100% Citric acid Citric Acid USP Granular, DSM Laureth-5 carboxylic acid Marlowet 1072, Sasol Germany GmbH Nutritional Products, Inc. Marl Citrus aurantifolia (lime) oil AEC Lime Oil, A & E Connock, Lauric acid Prifrac 2920, Croda Europe, Ltd. Perfumery & Cosmetics Ltd. 15 Lauryl glucoside Plantacare 1200 UP, BASF Cognis, 50% Cistus incantis extract; TEGO Pearl N300, Evonik Industries AG Lecithin AEC Lecithin Powder, A & E Connock, Maltodextrin Perfumery & Cosmetics Ltd. Cocamide DEA REWOMID DC 212 S, Evonik Industries Limonene Dipentene No. 122, Hercules Inc. AG, 100% Linalool Lipofresh, Lipo Chemicals, Inc. Cocamide MEA REWOMID D 212, Evonik Industries AG, Magnesium chloride OriStar MCL. Orient Stars LLC OO% Maltodextrin Farmal MD 10, Corn Products Cocamidopropyl betaine TEGO Betain F 50, Evonik Industries AG, 2O international 38% Malva Sylvestris leaf extract Herbasec Mallow Leaves, Cosmetochem Coco glucoside Plantacare 818 UP, BASF Cognis, 51% international AG Coco betaine Dehyton AB 30, BASF Cognis, 31% Mangifera indica (mango) Mango Extract, Draco Natural Products Coumarin Rhodiascent extra pure, Rhodia Organics fruit extract Creatine TEGO Cosmo C 100, Evonik Industries Menthol OriStar HSB, Orient Stars LLC AG, 100% 25 MIPA-Laureth Sulphate Zetesol 2056, Zschimmer & Schwarz Decylglucoside Plantacare 2000 UP, BASF Cognis GmbH Dicaprylylether Cetiol OE, BASF Cognis Octopirox Octopirox, Clariant Intl. Ltd. Dehydroacetic acid Unisept DHA (Universal Preserv-A- Olea europaea (olive) fruit oil Cropure Olive, Croda Europe, Ltd. Chem, Inc.) Palmitamidopropyltrimonium VARISOFT PATC, Evonik Industries AG, Dimethicone DC 200 Fluid 100 cst, Dow Corning, chloride) 60% OO% 30 Panthenol D-Panthenol USP, BASF, 100% Disodium REWOTERIC (RAM 2 CNM, Evonik PEG-120 Methylglucose ANTIL 120 Plus, Evonik Industries AG, cocoamphodiacetate industries, 39%-ig dioleate OO% Disodium cocoylglutamate Planatpon ACG LC, BASF Cognis PEG-14M Polyox WSR-205, The Dow Chemical Disodium EDTA Dissolvine NA-2-P, AkzoNobel Global Company Personal Care PEG-18 Castor oil dioleate MarlowetCG, Sasol Germany GmbH Disodium lauryl REWOPOL SBF 12 P. Evonik Industries as PEG-18 Glyceryl oleate? ANTIL 171 Plus, Evonik Industries AG, Sulphosuccinate AG, 95% cocoate OO% Ethylhexyl stearate: TEGO (R) Wipe Flex (Evonik Industries PEG-200 Hydrogenated REWODERM LIS 80, Evonik Industries Phenoxyethanol: AG) glyceryl palmate; PEG- AG, 100% Polyglyceryl-4 laurate; 7 Glyceryl cocoate Sorbitan laurate: PEG-3 Distearate TEGIND 1102, Evonik Industries AG, Dilauryl citrate 00%; Cutina TS, BASF Cognis, 100% Geraniol Nerol 800, International Flavors & 40 PEG-40 Hydrogenated TAGAT L 40, Evonik Industries AG, Fragrances Inc. castor oil OO% Glucose Organic Biovert Substrate, Lonza PEG-40 Sorbitan peroleate Arlatone T. Croda Glycerol Glycerol EP, vegetable, Spiga Nord, PEG-6 Caprylic?capric TEGOSOFT DEC, Evonik Industries AG, 99.7% glycerides OO% Glyceryl caprylate Dermosoft GMCY, Dr. Straetmans PEG-7 Glyceryl cocoate TEGOSOFT GC, Evonik Industries AG, Glycerylglucoside Hydagen GG, BASF Cognis 45 OO% Glyceryl oleate TEGINOV, Evonik Industries AG, 100% Perseagratissina Cropure Avocado, Croda Europe, Ltd. Glycine Soya (soybean) oil Cropure Soybean, Croda Europe, Ltd. (avocado) oil Glycol distearate TEGING 1100, Evonik Industries AG, Petrolatum Merkur 115, Sasol Wax GmbH 100% Phenethyl alcohol Etaphen, Vevy Europe SpA Guar Cosmedia Guar C 261, BASF Personal Phenoxyethanol S&M Phenoxyethanol, Schilke & Mayr hydroxypropyltrimonium Care and Nutrition Gmbh/Jaguar C-17, 50 GmbH chloride Rhodia Inc. and andere Phenoxyethanol; Ethylhexyl Euxyl PE 9010, Schilke & Mayr GmbH Helianthus annuit is AEC Sunflower Oil, A&E Connock, glycerol (sunflower) seed oil Perfumery & Cosmetics Ltd. Phenoxyethanol: Euxyl K300, Schuelke & Mayr GmbH Hydrogenated castor oil Cutina HR Powder, BASF Personal Care Methylparaben; and Nutrition Gmbh Ethylparaben; Butylparaben; Hydrolysed collagen Nutrilan H, BASF Personal Care and 55 Propylparaben; Nutrition Gmbh Sobutylparaben Hydrolysed keratin Kerasol, Croda, Inc. Polyatinopropy biguanide Microcare MBG, Thor olyglyceryl-3 palmitate Dermofeel PP, Dr. Straetmans Hydrolysed wheat protein Gluadin WLM, BASF Cognis C olyglyceryl-4 caprate TEGOSOFT PC-41, Evonik Industries Hydrolysed wheat starch Cropeptide W, Croda, Inc. AG, 100% Hydroxyethyl ethylcellulose Structure Cel 4400 E, AkzoNobel Global Polyglyceryl-6 caprylate: TEGO Betain 55, Evonik Industries AG Personal Care Polyglyceryl-4 caprate; 35% Hydroxypropyl guar Jaguar C-162, Rhodia, 100% Propylene glycol hydroxypropyltrimonium Polyguatemium-10) Polymer JR 400, Amerchol, 100% chloride Polyduatemium-11 Dehyguart CC 11, BASF Personal Care Hydroxypropyl TEGOCEL HPM 50, Evonik Industries and Nutrition Gmbh Luviguat PQ 11 PN, methylcellulose AG, 100% BASF Corporation Sopropyl myristate TEGOSOFTM, Evonik Industries AG, 65 Polyguaternium-37 Cosmedia Ultragel 300, BASF Personal 100% Care and Nutrition Gmbh US 9,409,853 B2 29 30 TABLE 42-continued TABLE 42-continued

List of raw materials used List of raw materials used

INCI Trade name, company INCI Trade name, company Polyguaternium-7 Merquat 550, Nalco, 100% Zinc PCA Zincidone, UCIB, Solabia Group Polysorbate 20 TEGO SML 20, Evonik Industries AG, Zinc pyrithione Microcare ZP, THORPERSONAL CARE 100% SAS Potassium sorbate Euxyl K 712, Schilke & Mayr GmbH Propylene glycol Euxyl K320, Schilke & Mayr GmbH Propylene glycol; PEG-55 ANTIL 141 Plus, Evonik Industries AG, 10 While the present invention has been particularly shown Propylene glycol oleate 100% Prints amygdalus duticis Cropure Almond, Croda Europe, Ltd. and described with respect to various embodiments thereof, it (Sweet almond) oil will be understood by those skilled in the art that the forego Prunus cerasus (bitter cherry) Prunus Cerasus Fruit, Kirschen Extract, ing and other changes in forms and details may be made fruit extract Botanica GmbH without departing from the spirit and scope of the present Ricinus communis seed oil Lipovol CO, Lipo Chemicals 15 Salicylic acid OriStar HSB, Orient Stars LLC invention. It is therefore intended that the present invention Silica Aerosil 130, Evonik Degussa GmbH not be limited to the exact forms and details described and Silicone quaternium-22 ABILT Quat 60, Evonik Industries AG, 65% illustrated, but fall within the scope of the appended claims. Silicone quaternium-22; ABILB 45, Evonik Industries AG, 30% Polyglycerol-3 caprate; What is claimed is: Dipropylene glycol; Cocamidopropyl betaine 1. A polyglycerol partial ester of general formula I Simmondsia chinensis AEC Jojoba Oil Refined, A & E Connock, (jojoba) seed oil Perfumery & Cosmetics Ltd. Sodium benzoate Euxyl K 712, Schilke & Mayr GmbH general formula I Sodium C14-16 olefin Bioterge AS-40 AOS, Stepan Sulphonate 25 Sodium cetearyl Sulphate Lanette E, BASF Personal Care and Nutrition Gmbh OR2 Sodium cocoamphoacetate REWOTERIC AMC, Evonik Industries AG, 32% Sodium REWOTERIC AM KSF 40, Evonik where cocoamphopropionate industries AG, 40% 30 Sodium coco Sulphate Texapon HC G, BASF Cognis n=2 to 16, Sodium cocoyl glutamate Plantapon ACG HC, BASF Cognis R", R. R.-are, independently of one another, identical or Sodium cocoylglycinate Hostapon SG, Clariant; Amilite GCS-11, Ajinomoto different, selected from H. R. and R, where Sodium cocoyl sarcosinate Crodasinic MS, Croda R-saturated or unsaturated acyl residue having 6-22 car Sodium disodium cocoyl PERLASTAN (R) SC 25 NKW, 35 bon atoms and comprising no hydroxyl groups, glutamate Schill&Seilacher, 25%, Sodium hydroxide Unichem SOHYD, Universal Preserv-A- R-saturated or unsaturated acyl residue having 6-22 car Chem, Inc. bonatoms and comprising at least one hydroxyl group or Sodium hydroxypropyl Pure-Gel, Grain Processing Corporation an acyl residue of an oligomer of Saturated or unsatur starch phosphate ated acyl residues having 6-22 carbon atoms and com Sodium isethionate Hostapon SI, Company Clariant international Ltd 40 prising at least one hydroxyl group, Sodium lactate Sodium Lactate Solution About 50%, wherein the acyl residues R* to Rare present in a molar Merck KGaAEMD Chemicals, Inc. ratio in a range of 95:5 to 5:95. actate; Sodium LACTIL, Evonik Industries AG, 100% PCA: Glycine; Fructose; 2. The polyglycerol partial ester according to claim 1, Urea; Niacinamide; Inositol; wherein R* and Rare acyl residues of fatty acids. Sodium benzoate: Lactic acid 45 3. The polyglycerol partial ester according to claim 1, aureth Sulphate Texapon NSO, BASF Cognis, 28% wherein at least 50 mol% of the Racyl residues are selected auroamphoacetate Cola Teric SLAA, Colonial Chemical Inc auroylisethionate Yongan SLI, Huanggang Yongan from capryloyl, caproyland lauroyl residues, based on all R' Pharmaceutical Co., Ltd residues in the polyglycerol partial ester. Sodium lauroyl methyl Iselux, Innospec Active Chemicals 4. The polyglycerol partial ester according to claim 1, isethionate 50 wherein R is selected from ricinoyl and hydroxystearoyl Sodium lauryl Sulphate Texapon LS35, BASF Cognis, 30% Sodium trideceth Sulphate Rhodapex EST-30, Rhodia residues, their oligomers and mixtures thereof. Sorbitan caprylate Sorbon S-10, Toho Chemical Industry Co., 5. The polyglycerol partial ester according to claim 1, Ltd. wherein at least 90 mol% of the Racyl residues comprise Sorbitan Sesquicaprylate) ANTIL Soft SC, Evonik Industries AG, ricinoyl residues or a mixture of ricinoyland hydroxy Stearoyl 100% 55 Stearic acid Pristerene 4922, Croda Europe, Ltd. residues, based on all R residues in the polyglycerol partial Styrene? acrylates copolymer Neolone PE, The Dow Chemical ester. Company 6. The polyglycerol partial ester according to claim 1, Sucrose cocoate TEGOSOFT LSE 65 K, Evonik Industries wherein R is selected from ricinoyl residues. AG, 100% 7. The polyglycerol partial ester according to claim 1, Tetrasodium EDTA Neolone PE, The Dow Chemical Company 60 wherein a weight ratio of the polyglyceryl residue to the Sum Tocopherol Euxyl K 700, Schilke & Mayr GmbH total of the acyl residues RandR is 85:15 to 55:45. Trideceth-9 Marlipal O 13790, Sasol Germany GmbH - 8. A method for preparing polyglycerol partial esters com Marl Tritictim vulgare germ oil Cropure Wheatgerm, Croda Europe, Ltd. prising the steps of: Xanthan gum Keltrol CG-SFT, CP Kelco, 100% A) providing a polyglycerol having a mean degree of poly Zea mays (corn) germ oil AEC Corn Germ. Oil, A & E Connock, 65 merisation n=2 to 16, Perfumery & Cosmetics Ltd. B) acylating some of the hydroxyl groups of the polyglyc erol with US 9,409,853 B2 31 32 at least one first carboxylic acid derivative of one or more acid, capric acid and lauric acid, based on the acyl residues of first, Saturated or unsaturated carboxylic acids having all the first carboxylic acid derivatives. 6-22 carbon atoms and comprising no hydroxyl groups, 11. The method according to claim 8, wherein at least 90 and mol % of the second carboxylic acids are selected from rici at least one second carboxylic acid derivative of one or 5 noleic acid and hydroxy Stearic acid, based on the acyl resi more second, Saturated or unsaturated carboxylic acids dues of all the second carboxylic acid derivatives. having 6-22 carbon atoms and comprising at least one 12. The method according to claim 8, wherein at least 90 hydroxyl group or an oligomer of the second carboxylic mol% of the second carboxylic acids comprise ricinoleic acid acid, and hydroxyStearic acid, and the second carboxylic acids said carboxylic acid derivatives are selected from carboxy 10 lic acids and carboxylic esters, and have a molar ratio of ricinoleic acid residues to hydroxys wherein a molar ratio of the acyl residues of the first car tearic acid residues in a range of 100 to 0.1 to 50 to 50, based boxylic acid derivative to those of the second carboxylic on the acyl residues of all the second carboxylic acid deriva acid derivative is in a range of 95.5 to 5:95. tives. 9. The method according to claim 8, wherein during said 15 13. The method according to claim 8, wherein a weight acylating ratio of the polyglycerol to the sum total of the acyl residues at least one first carboxylic acid and at least one second of the first and second carboxylic acid derivatives used is carboxylic acid, 85:15 to 55:45. at least one first carboxylic ester and at least one second 14. The method according to claim 8, wherein a molar ratio carboxylic acid, of the acyl residues of saturated to unsaturated carboxylic at least one first carboxylic acid and at least one second acid derivatives used in said acylating is 99:1-1:99. carboxylic ester, 15. A polyglycerol partial ester obtained by a method at least one first carboxylic ester and at least one second according to claim 8. carboxylic ester, 16. A formulation comprising at least one polyglycerol at least one first carboxylic acid and at least one first car 25 partial ester according to claim 1. boxylic ester and at least one second carboxylic acid, 17. The formulation according to claim 16, comprising: at least one first carboxylic acid and at least one first car 0.1% by weight to 40% by weight of said polyglycerol boxylic ester and at least one second carboxylic ester, partial ester, at least one first carboxylic acid and at least one second 0.01% by weight to 40% by weight of oil-soluble sub carboxylic acid and at least one second carboxylic ester, 30 stance, and at least one first carboxylic ester and at least one second 10% by weight to 98% by weight of water. carboxylic acid and at least one second carboxylic ester, 18. A method comprising: O mixing at least one polyglycerol partial ester according to at least one first carboxylic acid and at least one first car at claim 1 with at least one oil-soluble substance to boxylic ester and at least one second carboxylic acid and 35 provide a mixture; and at least one second carboxylic ester, treating said mixture with water, wherein said at least one are used. polyglycerol partial ester solubilizes said least one oil 10. The method according to claim 8, wherein at least 50 Soluble Substance upon said treating with water. mol % of the first carboxylic acids are selected from caprylic k k k k k